JP2002131927A - Method for reusing inorganic powder for photosensitive paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the cost of photosensitive paste by recovering inorganic powder from waste developer after using the photosensitive paste and using the photosensitive paste again. SOLUTION: By using this inorganic powder recovering method, the photosensitive paste which has excellent developing ability and good pattern accuracy after development, where the residue of organic substance after calcination is little, and which has excellent adhesion is provided even in the case of using the inorganic powder recovered from the waste developer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is preferably used when a photosensitive paste (C) containing a photosensitive resin composition (A) and an inorganic powder (B) is used. The present invention relates to a method of recovering inorganic powder from waste liquid and reusing the same in a photosensitive paste.

[0002]

2. Description of the Related Art Conventionally, in manufacturing electronic parts, plasma display panels, etc., a resistor paste (resistor in paste form), a phosphor paste (phosphor in paste form), a partition paste (partition). Insulation paste (paste of insulator material) and conductor paste (paste of conductive material such as copper powder, silver powder, etc.) by pattern printing by screen printing etc. It is also known to form a resistor pattern, a phosphor pattern and a partition pattern, an insulator pattern or a conductor circuit pattern by baking, and these are recent resistor patterns, phosphor patterns, partition patterns. Or, it cannot cope with high-density, high-fine-line and high-precision patterning of the conductor circuit pattern. Therefore, photosensitive pastes have been studied for the purpose of increasing the density, thinning, and increasing the precision of the patterns of the formed resistors, phosphors, partition walls, insulators, and circuit conductors. This is done by applying a photosensitive paste to the entire surface of various substrates (eg, glass, ceramic, metal, etc.) by screen printing or the like, drying it, and exposing it to ultraviolet light using a negative mask that allows only the part to be patterned to pass ultraviolet light. Then, development is performed by spraying using water or a dilute alkaline aqueous solution, and then baking at 400 to 1000 ° C. for 1 to 24 hours to form a pattern.

[0003]

By using a photosensitive paste, the density, thickness, and precision of the pattern of the formed resistor, phosphor, partition, insulator or circuit conductor can be increased. However, by exposing and developing the photosensitive paste applied to the entire surface of the substrate, unnecessary paste is removed. Depending on the pattern to be formed, the amount of paste remaining as a pattern is 70% or less of the applied paste,
When the amount is small, it is 30% or less. In other words, 30 to 70% of the paste is discarded as a developing waste liquid, and an increase in cost is inevitable, which hinders the practical spread of the photosensitive paste.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and it is an object of the present invention to recover an inorganic powder from a developing waste liquid after using a photosensitive paste and re-use the photosensitive paste. To provide a method for reuse.
That is, (1) the inorganic powder is recovered from the waste developer after use of the photosensitive paste (C) containing the photosensitive resin composition (A) and the inorganic powder (B), and the photosensitive paste is again used. (2) the method of reusing the photosensitive paste according to the above (1), wherein the method of recovering the inorganic powder is a wet method comprising a washing step using a washing liquid, and (3) the washing liquid is water and / or (1) The method for reusing the photosensitive paste according to the above (1) or (2), wherein (4) the inorganic powder used in the photosensitive paste has a usage ratio of the recovered inorganic powder of 1
(5) The photosensitive resin composition (A) contains a polymer conjugate (D), a diluent (E), and a photopolymerization initiator (F). (6) an epoxy resin (G) in which the polymer conjugate has at least two or more epoxy groups in a molecule; an unsaturated double bond and a carboxyl group in one molecule. (H) and an unsaturated component obtained by reacting an epoxy (meth) acrylate which is a reaction product of a saturated monocarboxylic acid (I) as an optional component with a polybasic anhydride (J) if necessary The photosensitive paste according to the above (4) or (5), which is a group-containing resin,
(7) The photosensitive material as described in (4) or (6) above, wherein the inorganic powder (B) is one or more selected from metals, metal oxides, metal sulfides, and glass. (8) The resin composition according to the above (4) to (7) for a resistor pattern, a conductor pattern, an insulator pattern, a phosphor pattern or a partition pattern, (9) the above (4) to (8) (10) A cured product of the resin composition according to any one of (4) to (9), (11) a resistor and a conductor obtained by firing the cured product according to (10). , An insulator, a phosphor, and a partition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention provides a photosensitive resin composition (A) and an inorganic powder (B)
This is a method of recovering inorganic powder from the developing waste liquid after using the photosensitive paste (C) composed of the above, and reusing the inorganic powder again for the photosensitive paste. The method of recovering the inorganic powder from the development waste liquid is roughly classified into a wet method and a dry method,
Either may be used. In the dry method, the waste developer is heated,
This is a method in which a photosensitive resin composition component and a developer component are removed by heating to recover inorganic powder. When a dry method is specifically exemplified, it is preferable that the waste developer is allowed to stand, the inorganic powder is settled, the supernatant is discarded, and then heating is performed. Heating temperature is 1
The temperature is preferably from 00 to 1000 ° C, more preferably from 200 to
~ 800 ° C, preferably lower than the sintering temperature of the inorganic powder, and a temperature at which the photosensitive resin composition components are easily decomposed by heating and removed.

On the other hand, the method of recovering inorganic powder by a wet method comprises a washing step using a washing liquid such as a solvent. The solvent to be used is not particularly limited, and is preferably an organic solvent, water and / or a developer. Organic solvents include ketones such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, ethylene glycol monoaryl ethers, polyethylene glycol monoaryl ethers, acetone, methyl ethyl ketone, and methyl isobutyl ketone. , Acetates, esters such as butyl acetate, toluene, xylene, aromatic hydrocarbons such as benzyl alcohol, propylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, ethylene carbonate, Examples include propylene carbonate, γ-butyrolactone, and solvent naphtha.

When the photosensitive resin composition is water-developable, the washing solution is preferably water. When the photosensitive resin composition is dilute alkali-developable, sodium carbonate, potassium carbonate, monoethanolamine, diethanolamine, triethanolamine, sodium hydroxide, and sodium hydroxide are used. An aqueous solution of about 0.1 to 10% such as potassium or tetramethylammonium hydroxide is preferable. The temperature of the washing liquid is preferably 10 to 80 ° C., and it is preferable to stir during the washing, and then it is preferable that the washing liquid is allowed to stand to separate the inorganic powder and the washing liquid. The washing is preferably performed repeatedly, particularly preferably 2 to 20 times. Moreover, when washing with an organic solvent or a developing solution, washing with water is preferred.

After the washing step, the inorganic powder may be separated from the washing liquid by filtration or the like and dried. Drying is performed using a far-infrared ray or hot air dryer, and the drying temperature is 30 to 200 ° C.
The drying time is preferably 1 to 100 hours.

The photosensitive resin composition (A) used in the photosensitive paste of the present invention preferably contains a polymer conjugate (D), a diluent (E), and a photopolymerization initiator (F). The polymer conjugate (D) includes (meth) acrylic resin, polyester resin, polyether resin, polyurethane resin, polycarbonate resin, polyacetal resin, cellulose resin, polyvinyl alcohol, and the like, and the molecular weight is preferably from 1,000 to 200,000. When it has an acid value, the acid value is preferably from 10 to 200. In particular, the polymer conjugate (D) includes an epoxy resin (G) having at least two or more epoxy groups in a molecule and a compound (H) having one unsaturated double bond and one carboxyl group in one molecule. As an optional component, an unsaturated group-containing resin obtained by reacting an epoxy (meth) acrylate which is a reaction product with a saturated monocarboxylic acid (I) and, if necessary, a polybasic acid anhydride (J) is preferable.

Specific examples of the compound (G) having two or more epoxy groups in one molecule used in the present invention include a bisphenol A type epoxy resin (for example, Epicoat Co., Ltd., manufactured by Yuka Shell Epoxy Co., Ltd.). 828, Epicoat 1001, Epicoat 1002, Epicoat 1004
Etc.), an epoxy resin obtained by a reaction between an alcoholic hydroxyl group of a bisphenol A type epoxy resin and epichlorohydrin (eg, NER-1302, manufactured by Nippon Kayaku Co., Ltd.)
Epoxy equivalent 323, softening point 76 ° C), bisphenol F type resin (eg, manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 807, EP-4001, EP-4002, EP-4)
004), an epoxy resin obtained by a reaction between an alcoholic hydroxyl group of a bisphenol F type epoxy resin and epichlorohydrin (eg, NER-74 manufactured by Nippon Kayaku Co., Ltd.)
06, epoxy equivalent 350, softening point 66 ° C.), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg, YX-400 manufactured by Yuka Shell Epoxy Co., Ltd.)
0), phenol novolak type epoxy resin (eg, Nippon Kayaku Co., Ltd., EPPN-201, Yuka Shell Epoxy Co., Ltd., EP-152, EP-154, Dow Chemical Co., Ltd., DEN-438) ), Cresol novolak type epoxy resin (eg, Nippon Kayaku Co., Ltd., EOCN-102)
S, EOCN-1020, EOCN-104S), triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd., TE
PIC), trisphenol methane type epoxy resin (Nippon Kayaku Co., Ltd., EPPN-501, EPN-502,
EPPN-503), fluorene epoxy resin (eg, Nippon Steel Chemical Co., Ltd., cardo epoxy resin, ESF-30)
0), alicyclic epoxy resin (Daicel Chemical Industries, Ltd.)
Made, Celloxide 2021P, Celloxide EHPE)
And the like.

Another example of (G) is a copolymerizable epoxy resin. As a copolymer type epoxy resin,
For example, glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide, and other monofunctional ethylenically unsaturated group-containing compounds (eg, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate,
(Meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α
-Methylstyrene, glycerin mono (meth) acrylate, general formula (1)

[0012]

Embedded image

(Wherein R ₁ is hydrogen or an ethyl group, R ₂ is hydrogen or a C ₁ -C ₆ alkyl group, and n is an integer of 2 to 23) And a copolymer obtained by reacting the above. Specifically, CP-15, CP-30, CP-50, C manufactured by NOF Corporation
P-20SA, CP-510SA, CP-50S, CP
-50M, CP-20MA, etc.). Examples of the compound of the formula (1) include polyethylene glycol mono (meth) acrylate such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate, and methoxydiethylene glycol mono (meth) acrylate. Examples include alkoxy polyethylene glycol (meth) acrylate such as acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

The molecular weight of the copolymerizable epoxy resin is about 1
000 to 200,000 is preferred. Glycidyl (meta)
The use amount of the acrylate is preferably from 10 to 70% by weight, particularly preferably from 20 to 50% by weight, based on the total amount of unsaturated monomers used in the copolymerizable epoxy resin.

When a copolymerizable epoxy resin which can be developed with water is obtained, glycerin mono (meth) acrylate and / or the compound of the general formula (1) is added to the total amount of unsaturated monomers used in the polymer. On the other hand, it is desirable to add 30% by weight or more, particularly preferably 50% by weight or more.

The copolymerizable epoxy resin can be obtained by a known polymerization method, for example, solution polymerization or emulsion polymerization. To explain the case of using solution polymerization,
The ethylenically unsaturated monomer mixture is added to a polymerization initiator in an applicable organic solvent, and is preferably added under a nitrogen stream under a nitrogen stream.
The polymerization is carried out by heating and stirring at 00 ° C. Examples of the organic solvent include ethanol, propanol,
Isopropanol, butanol, isobutanol, 2-
Alcohols such as butanol, hexanol and ethylene glycol, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve,
Carbitols such as carbitol and butyl carbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol Examples thereof include acetic esters such as monomethyl acetate, lactic esters such as ethyl lactate and butyl lactate, and dialkyl glycol ethers. These organic solvents can be used alone or in combination.

As the polymerization initiator, for example, a peroxide such as benzoyl peroxide and an azo compound such as azobisisobutyronitrile can be used.

Examples of the compound (H) having one unsaturated double bond and one carboxyl group in one molecule include (meth) acrylic acid and hydroxyl group-containing (meth) acrylate (for example,
Acid anhydrides of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compounds (for example, succinic anhydride, maleic anhydride) Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.).

Specific examples of the saturated monocarboxylic acid (I) include acetic acid, propionic acid, pivalic acid, hydroxypivalic acid, dimethylolpropionic acid, benzoic acid, and hydroxybenzoic acid.

The compound (H) and the saturated monocarboxylic acid (I) as an optional component are preferably reacted in an amount of 0.5 to 1.1 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin (G). Also, a reaction solvent may be used if necessary,
For example, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, alcohols such as ethylene glycol, methyl ethyl ketone, ketones such as cyclohexanone, toluene, aromatic hydrocarbons such as xylene, cellosolve,
Cellosolves such as butyl cellosolve, carbitols such as carbitol and butyl carbitol, propylene glycol alkyl ethers such as propylene glycol methyl ether, polypropylene pyrene glycol alkyl ethers such as dipropylene glycol methyl ether, ethyl acetate, butyl acetate And acetates such as cellosolve acetate and propylene glycol monomethyl acetate, lactates such as ethyl lactate and butyl lactate, and dialkyl glycol ethers. These organic solvents can be used alone or as a mixture.

In order to promote the reaction, a basic compound such as triphenylphosphine, triphenylstibine, triethylamine, triethanolamine, tetramethylammonium chloride, benzyltriethylammonium chloride or the like is added to the reaction solution in an amount of 0.1 to 10%. 1
% Is preferably added. During the reaction, it is preferable to add a polymerization inhibitor (for example, methoxyphenol, methylhydroquinone, hydroquinone, phenothiazine, etc.) in the reaction solution in an amount of 0.05 to 0.5% in order to prevent polymerization.
The reaction temperature is preferably 90 to 150 ° C, and the reaction time is preferably 5 to 40 hours.

If necessary, an acid anhydride (J) of a polycarboxylic acid compound (for example, succinic anhydride, maleic anhydride, anhydride, etc.) is added to one equivalent of the hydroxyl group of the epoxy (meth) acrylate thus obtained. Phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) can be reacted preferably in an amount of from 0.2 to 1.0 equivalent of an anhydride group.
The reaction temperature is preferably 90 to 150 ° C, and the reaction time is preferably 3 to 30 hours.

In the present invention, a diluent (E) is used.
Specific examples of the component (E) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloyl Acid anhydride of morpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compound (E.g., succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) half ester, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, Methylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxytri (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopyrene glycol hydroxybivalate (for example, KAY manufactured by Nippon Kayaku Co., Ltd.
ARAD HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, mono or polyglycidyl Compounds (for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Epoxy which is a reaction product of (meth) acrylic acid with hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc. Reactive diluents (E-1) such as meth) acrylates, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers,
Diethylene glycol monoalkyl ether acetates, ethylene glycol monoaryl ethers, polyethylene glycol monoaryl ethers, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetates, esters such as butyl acetate,
Toluene, xylene, aromatic hydrocarbons such as benzyl alcohol, propylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, ethylene carbonate, propylene carbonate,
Organic solvents (E-2) such as γ-butyrolactone and solvent naphtha can be exemplified. The diluents may be used alone or as a mixture of two or more.

Specific examples of the photopolymerization initiator (F) include, for example, 2,4-diethylthioxanthone, 2-chlorocutixanthone, isopropylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propane-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide, Michler's ketone, benzyldimethyl ketal, and 2-ethylanthraquinone. Further, a photopolymerization accelerator (for example, amines such as N, N-dimethylaminobenzoic acid ethyl ester and N, N-dimethylaminobenzoic acid isoamyl ester) as an accelerator of the photopolymerization initiator (F) is used in combination. You can also.

Specific examples of the metal powder, metal oxide powder, metal sulfide and / or glass (B) used in the present invention are preferably ruthenium oxide, yttrium oxide, europium oxide, samarium oxide having a particle size of 10 μm or less. , Cerium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, Y ₂ O ₂ : Eu, YVO ₄ : Eu, (Y, Gd)
BO ₃ : Eu, BaAl ₁₂ O ₁₉ : Mn, Zn ₂ SiO
₄ : Mn, BaMgAl ₁₄ O ₂₃ : Eu, BaMgAl ₁₆
O ₂₇ : Eu, MgO, LaB ₆ , Al, La _0.5 Sr _0.5
Metal oxides such as CoO ₃ , La _0.7 Sr _0.3 : MnO ₃ , (Zn, Cd) S: Ag, (Zn, Cd) S: Cu
Metal sulfide, copper powder, silver powder, palladium powder, mixed powder of silver and palladium, surface-treated gold powder, lanthanum, cerium, samarium, praseodymium, neodymium, promethium, europium, gadolinium, terbium, dysprosium, holmium, thulium , Erbium, ruthenium, yttrium, scandium and other metal powders, glass powders, glass beads and the like. Due to the properties of these, they can be applied to a composition for a resistor, a composition for a conductor circuit, a resin composition for an insulator, a composition for a phosphor, a composition for a partition, and the like. Can also.

The photosensitive paste (C) of the present invention comprises (A)
And (B) can be prepared by dissolving, mixing and kneading the components. (A) is (D), (E),
(F) and may be used in the form of a photosensitive varnish.
In the photosensitive paste of the present invention, the use ratio of each component can be as follows (% is% by weight). (D) + (E
-1) + (F) is used in a total amount of 5 to 5 with respect to the composition.
It is preferably 60%, particularly preferably 10 to 50%. The component (B) is preferably 40 to 95%, particularly preferably 50 to 90%, of the composition. (D) + (E
The preferred amount of each component in the total amount of (-1) + (F) is 30 to 90% of the component (D), and (E)
The amount of component -1) used is 5 to 65%, and the amount of component (F) used is 5 to 30%. The amount of the organic solvent (E-2) can be used in any ratio for the purpose of adjusting the viscosity and the like suitable for using the composition of the present invention.

In the photosensitive paste of the present invention, a leveling agent, an antifoaming agent, a coupling agent, a polymerization inhibitor, a wax, etc. may be used as long as the performance is not impaired.

In the inorganic powder used in the photosensitive paste used in the present invention, the ratio of unused inorganic powder to recovered inorganic powder is preferably 1 to 100% by weight,
20 to 80% by weight is preferred. If the ratio of the unused inorganic powder is large, the cost does not decrease, which is not preferable.

As described above, the resin composition of the present invention comprises a composition for a resistor, a resin composition for a phosphor, a resin composition for a partition,
It can be used as a resin composition for a conductor circuit or a resin composition for an insulator, and these can be used on various substrates (for example, glass, ceramic, metal, etc.) by a method such as screen printing, curtain flow coating, or spray coating. It is applied on the whole surface. After the application, if necessary, pre-baking is performed at about 50 to 250 ° C. with far infrared rays or warm air to remove the organic solvent, and then the film is exposed to ultraviolet rays using a negative mask that allows only the portions to be patterned to pass ultraviolet rays. The amount of exposure to ultraviolet light is preferably from 10 to 1000 mJ / cm ² . Next, development is performed by means such as spraying with water or a dilute aqueous alkali solution at a liquid temperature of 10 to 60 ° C.
Baking at １０００1000 ° C. for 1１〜24 hours to form a pattern.

When used as a film, the resin composition of the present invention is applied to a release film using a wire bar method, dipping method, spin coating method, gravure method, doctor blade method, or the like. It is dried at 50 to 250 ° C. by far-infrared rays or warm air as needed, and a release film or the like is attached as needed. When using, peel off the release film and transfer it to the substrate,
A pattern is formed by exposure, development, and baking as described above.

[0031]

The present invention will be described below with reference to Examples 1 to 11. In the examples, “parts” means “parts by weight”. According to the compositions shown in Tables 1 to 3, conductors, phosphors, and photosensitive pastes for partition walls were prepared. Using a guide, apply the obtained resin composition to the entire surface of the glass substrate at a thickness of 130 μm (dry thickness),
After pre-baking at 80 ° C. for 30 minutes, a negative film (line / space = 150 μm / 150 μm) is brought into contact, irradiated with 1500 mJ / cm ² by an ultra-high pressure mercury lamp, and then the unexposed part is developed using a developing solution (40 ° C.). Spray pressure 2kg / cm ²
For 2 minutes. After the development, baking was performed at 500 ° C. for 1 hour in the air to form partition walls and a phosphor pattern. Resin content in pattern, developability, state of pattern after development,
The adhesion to the glass substrate after firing was evaluated.

Next, the inorganic powder was recovered. The photosensitive paste is dried at 80 ° C. for 1 hour, dissolved in a developer,
After standing for 15 minutes, the inorganic powder was settled and the supernatant was discarded. This operation was repeated twice, the developer was changed to water, and the washing was repeated three more times, followed by drying at 100 ° C. overnight.
When the collected inorganic powder was observed by SEM, the particle size,
There was no change in shape. Using the recovered inorganic powder, photosensitive pastes similar to those in Tables 1 to 3 were prepared and evaluated. The results were the same as those in Tables 1 to 3.

Synthesis Example 1 (Synthesis example of reactant A) A trisphenolmethane-type epoxy resin (EPPN-503, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200, (Softening point 83 ° C) 200 parts, acrylic acid 72
, 0.2 parts of methylhydroquinone and 169.1 parts of propylene glycol monomethyl ether acetate, and the mixture was heated to 90 ° C. and dissolved. Then, the mixture was cooled to 60 ° C. and charged with 1.2 parts of triphenylphosphine.
After reacting for 32 hours, tetrahydrophthalic anhydride 1
12.6 parts were charged and reacted at 95 ° C. for 15 hours to obtain an unsaturated group-containing polycarboxylic acid resin having a solid content acid value (mg KOH / g) of 100.

Synthesis Example 2 (Synthesis example of reactant (A)) A round-bottomed flask equipped with a stirring device and a condenser was charged with a copolymerizable epoxy resin (Nippon Yushi Co., Ltd., Blenmer CP-50M, epoxy equivalent 31).
0, average molecular weight 6000) 310 parts, acrylic acid 72
, 0.3 parts of methylhydroquinone and 244.5 parts of propylene glycol monomethyl ether acetate, and the mixture was heated to 60 ° C. and dissolved. Then, the mixture was cooled to 60 ° C., and 1.8 parts of triphenylphosphine was charged.
After reacting for 32 hours at 70 ° C., 70 parts of succinic anhydride was charged and reacted at 95 ° C. for 15 hours to obtain a solid acid value (mg KO).
H / g) 80 unsaturated group-containing polycarboxylic acid resin was obtained.

(Synthesis Example of Reactant (A)) Synthesis Example 3 70 parts of glycerol methacrylate, 30 parts of glycidyl methacrylate, 100 parts of carbitol acetate, and 3 parts of benzoyl peroxide were added, and heated at 75 ° C. under a nitrogen stream. Polymerization was carried out for 5 hours to obtain a 50% polymer solution. Next, 300 parts of this 50% polymer solution, 22.8 parts of acrylic acid, and 0.16 of methylhydroquinone were added.
, 0.9 part of triphenylphosphine and 250 parts of carbitol acetate were mixed and dissolved, and reacted at 95 ° C. for 32 hours to obtain a reaction product solution. The average molecular weight of the reactants is about 1
It was 20,000.

Synthesis Example 4 50 parts of tetraethylene glycol monomethacrylate,
25 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, 100 parts of propylene glycol monomethyl ether acetate, and 2 parts of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen stream, polymerized at 75 ° C. for 5 hours, and a 50% polymer solution was obtained. Obtained. Then, this 50%
300 parts of polymer solution, 19 parts of acrylic acid, 0.16 part of methylhydroquinone, 0.9 parts of triphenylphosphine
Parts, 250 parts of carbitol acetate were mixed and dissolved,
The reaction was performed at 95 ° C. for 32 hours to obtain a reaction solution. The average molecular weight of the reaction was about 80,000.

Synthesis Example 5 70 parts of methoxytetraethylene glycol monomethacrylate, 30 parts of glycidyl methacrylate, 100 parts of carbitol acetate and 3 parts of benzoyl peroxide were added, and the mixture was heated at 75 ° C. and polymerized at 75 ° C. for 5 hours. A 50% polymer solution was obtained. Then, 300 parts of this 50% polymer solution, 22.8 parts of acrylic acid, 0.16 part of methylhydroquinone, 0.9 part of triphenylphosphine
Parts, 250 parts of carbitol acetate were mixed and dissolved,
The reaction was performed at 95 ° C. for 32 hours to obtain a reaction solution. The average molecular weight of the reaction product was about 170,000.

Table Examples Example 1 2 3 4 Polymer obtained in Synthesis Example 1 15.4 15.4 7.7 Polymer obtained in Synthesis Example 2 15.4 7.7 KAYARAD PEG400DA * 175 5 KAYARAD DPHA * 22 2 KAYARAD DPCA-60 * 3 27 KAYACURE DETX-S * 42 2 22 KAYACURE EPA * 52 22 2 Silver powder 40 40 40 Glass beads 40 Propylene glycol monomethyl ether acetate 35 35 35 35 35 Residual organic matter (wt%) 0.1 0.1 0.05 0.05 Developability (1 % Aqueous sodium carbonate solution) ○ ○ ○ ○ State of pattern after development ○ ○ ○ ○ Adhesion ○ ○ ○ ○

Table 2 Example 5 6 7 8 Polymer obtained in Synthesis Example 3 22.7 17.0 Polymer obtained in Synthesis Example 4 22.8 Polymer obtained in Synthesis Example 5 20.0 Diacrylate of tetraethylene glycol diglycidyl ether 2 2 118 KAYARAD PEG400DA 75 KAYARAD DPHA 22 KAYACURE DETX-S 222 2 KAYACURE EPA 222 2 22 Silver powder 30 30 30 Copper powder 30 Propylene glycol monomethyl ether acetate 37 37 39 39% 0.2 wt. 0.15 Developability (water) ○ ○ ○ ○ State of pattern after development ○ ○ ○ ○ Adhesion ○ ○ ○ ○

Table 3 Example 9 10 Polymer obtained in Synthesis Example 1 20 Polymer obtained in Synthesis Example 5 20 KAYARAD THE-330 * 6555 Irg-651 * 7 0.25 0.25 Phosphor powder 30 30 Residual organic matter (Wt%) 0.1 0.1 Developability (1% sodium carbonate aqueous solution) ○ Developability (water) ○ State of pattern after development ○ ○ Adhesion ○ ○

Note * 1 KAYARAD PEG400DA: polyethylene glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.) * 2 KAYARAD DPHA: dipentaerythritol penta and hexaacrylate (Nippon Kayaku Co., Ltd.)
* 3 KAYARAD DPCA-60: caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) * 4 KAYACURE DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) * 5 KAYACURE EPA: manufactured by Nippon Kayaku Co., Ltd.
p-Dimethylaminobenzoic acid ethyl ester * 6 KAYARAD THE-330: EO-modified trimethylolpropane triacrylate (Nippon Kayaku Co., Ltd.)
* 7 Irg-651: Ciba-Geigy Co., Ltd., 2,
2-dimethoxy-1,2-diphenylethan-1-one

Example 11 The photosensitive paste of Example 1 had a thickness of 130 μm after drying.
And then dried at 80 ° C. for 30 minutes to obtain a film. This film was transferred to a glass substrate, brought into contact with a negative film,
Irradiation was performed at 0 mJ / cm ² , and the unexposed area was developed with a 1% aqueous solution of sodium carbonate (40 ° C.) at a spray pressure of 2 kg / cm ² for 2 minutes. After development, bake in air at 500 ° C for 1 hour,
A partition pattern was formed. The residual resin content in the pattern, the developability, the state of the pattern after development, and the adhesion to the glass substrate after firing were all ○.

(Residual organic content): The weight loss after heating and baking at 500 ° C. for 60 minutes was measured. (Developability): An organic solvent-based developer was developed for 2 minutes at a liquid temperature of 40 ° C. and a spray pressure of 2 kg / cm ² The image was evaluated as follows: ○: Completely developed △: Slight residue ×: Some undeveloped part-: Part or all of the pattern Peeled off (state of pattern after development): ○ ・ ・ ・ ・ Pattern is accurately maintained △ ・ ・ ・ ・ Pattern width is narrow × ・ ・ ・ ・ ・ ・ Part of pattern part or , Completely peeled off (adhesion): Cellotape (registered trademark) peeling test was performed ..... No peeling was observed.

As is clear from the results of Examples 1 to 11, in the method of recycling the photosensitive paste of the present invention, even if the inorganic powder recovered from the waste developing solution is used, the developability is excellent, and after the development, A photosensitive paste having good pattern accuracy, little residual organic matter after firing, and excellent adhesion.

[0045]

According to the method for reusing a photosensitive paste of the present invention, even if inorganic powder recovered from a developing waste liquid is used, it has excellent developability, good pattern accuracy after development, and organic matter after firing. And a photosensitive paste having excellent adhesion can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 63/00 G03F 7/004 501 4J036 G03F 7/004 501 7/027 515 7/027 515 B09B 5/00 ZABZ F-term (reference) 2H025 AB15 AB16 AC01 AD01 BC13 BC74 BC83 BC85 CA00 CC08 CC15 CC20 FA28 FA29 2H096 AA30 BA05 BA06 LA25 LA30 4D004 AA16 AB01 AB05 BA06 CA42 CA50 4F071 AA42 AB07 AB28 AE17 AH12 BC014006 CDJ04006 AA01 CA20 CA21 FA01 FA10 FB03 FB10 FB11 FB12 FB18 HA02 JA09

Claims (11)

[Claims] An inorganic powder is recovered from a developing waste liquid after use of a photosensitive paste (C) containing a photosensitive resin composition (A) and an inorganic powder (B), and is re-formed into a photosensitive paste. How to use. 2. The method according to claim 1, wherein the method for recovering the inorganic powder is a wet method comprising a washing step using a washing liquid. 3. The method according to claim 1, wherein the cleaning solution is water and / or a developing solution. 4. The photosensitive paste according to claim 1, wherein the used proportion of the recovered inorganic powder is 1 to 100% by weight. 5. The photosensitive resin according to claim 4, wherein the photosensitive resin composition (A) contains a polymer conjugate (D), a diluent (E), and a photopolymerization initiator (F). Paste. 6. An epoxy resin (G) in which the polymer conjugate has at least two or more epoxy groups in a molecule and a compound (H) having one unsaturated double bond and one carboxyl group in one molecule. Saturated monocarboxylic acid (I) as an optional component
6. The photosensitive paste according to claim 4, wherein the resin is an unsaturated group-containing resin obtained by reacting an epoxy (meth) acrylate which is a reaction product with a polybasic acid anhydride (J) as required. . 7. The photosensitive material according to claim 4, wherein the inorganic powder (B) is one or more selected from metals, metal oxides, metal sulfides, and glass. paste. 8. A pattern for a resistor pattern, a conductor pattern, an insulator pattern, a phosphor pattern, or a partition pattern.
8. The resin composition according to any one of items 7 to 7. 9. A film comprising the resin composition according to claim 4. 10. A cured product of the resin composition according to claim 4. 11. A resistor, a conductor, an insulator, a phosphor and a partition wall obtained by firing the cured product according to claim 10.